1,1,2-trichloro-1-fluoroethane



Patented Dec. id, 1952 1,1,2-TRICHLORO-l-FLUOROETHANE William A. Stover, Woodbury, N. J assignor to Socony-Vacuum Oil Company, Incorporated, a

corporation of New York No Drawing. Application December 22, 1948, Serial No. 66,851

1 Claim.

This invention relates to the production of monofiuorochloroalkanes from chloroalkenes and to new compositions of matter produced thereby. It is more specifically concerned with product by a method which is eflicient and economical. It has now been found that by properly controlling the reaction conditions, hydrogen fluoride can be reacted with chlorothe production of 1,1,2-trichloro-l-fluoroethane olefins to produce good yields of monofluorofrom trichloroethylene. chloroalkanes.

The reaction of hydrogen fluoride with chloro- Accordingly, it is an object of the present inolefins is not new. As reported by Henne and vention to provide a process for the production Whaley, J. A. C. S. 64, 1157 (1942), Henne and of monofluorochloroalkanes which is efficient Haeckel, J. A. C. S. 63, 2692 (1941), Henne and and economical. Another object is to provide Renolt, J. A. C. S. 59, 2434 (1937) and Henne new compositions of matter. A specific object and Hinkamp, J. A. C. S. 67, 1194, 1197 (1945), is to provide 1,1,2-trich1oro-1-fluoroethane by a the following typical reactions have been studied: process wherein it is the predominant product. (1 CHa.CH:CCl;+HF CH2.CH.CFC12 Addition CH;.CH2.OF2C1 Addition and substitution (2 cm=ocrcmc1+nr CH3.OFCI.OH2C1 Addition CH3-CFLOH2G1 Addition and substitution (3) cmccnonfinr omorcrcn; Addition OH3.CFI.CH3 AddltlOIl and substitution 4 CHgzCCLOHpCHH-HF CH3OFC1.CH"CH3 Addition CH3 CECE; 3 Addition and substitution (5) CGl2:CH.CHz.CH3+HF cinch 011201120113 Addition Most of these reactions were carried out in the presence of an excess of hydrogen fluoride in the temperature range varying between C. and 100 C.

According to these authors, these reactions, in all cases, produced mixtures of the indicated products. Apparently, no attempt was made to influence the course of the reactions so as to produce either one or the other of the indicated products, exclusively, or in a large preponderance.

United States Letters Patent No. 2,399,024 to Jesse Harmon also describes the reaction of hydrogen fluoride with a chloro-olefln, trichloroethylene, and the production of a certain amount of 1,2-dichloro-1,1-difluoroethane as a result.

A paper presented before the Organic Section of the American Chemical Society at Atlantic City, April 9, 1946, by McBee, Hass, Bittenbender, Weesner, Toland and Hausch, and entitled Fluorinated. Derivatives of Ethane, also describes the reaction of hydrogen fluoride with certain choloro-oleflns and the production of diand tri-fluoroalkanes as a result.

In so far as can be determined, no attempt has heretofore been made to efiiiciently produce monofluorochloroalkanes from chloro-olefins by direct treatment of the chloro-olefins with hydrogen fluoride. Such a method of producing monofluorochloroalkanes is obviously advantageous, since it avoids thenecessity of using expensive fluorinating catalysts, such as the antimony fluorides and the mercury fluorides.

In accordance with the present invention, it has now been discovered that monofluorochloroalkanes can be produced as the predominant Addition and substitution Other objects and advantages of the present invention will become apparent to those skilled in the art from the following detailed description.

Broadly stated, the present invention provides a process for the production of monofiuorochloroalkanes having at least one chlorine atom attached to the same carbon atom to which the fluorine atom is attached, which comprises contacting a chloro-olefin having at least one double bond and at least one chlorine atom attached to a carbon atom which forms part of an unsaturated carbon-carbon linkage, with hydrogen fluoride, in a reaction zone, in a molar ratio of hydrogen fluoride to chloro-olefin of less than about 13:1 and, preferably, between about 7:1 and about 1:1, at a pressure of at least 2200 pounds per square inch, for a period of time of less than about ten hours, and, preferably, less than about five hours, and at temperatures varying between about C. andabout 325" C'.; and, as new compositions of matter, the 1,1,2- trichloro-l-fluoroalkanes produced thereby.

The chloro-olefin reactants utilizable in the present process are those having at least one double bond and at least one chlorine atom attached to a, carbon atom which forms part of an unsaturated carbon-carbon linkage. In this connection, any polychlorinated olefin which has chlorine atoms substituted at random throughout the molecule may be used provided that at least one chlorine atom is attached to a carbon atom which forms part of an unsaturated carbon-carbon linkage. Although any such olefin may be used, it is preferred to use chloro-olefins 1,2-dichlorooctene-1; dichloroconylene; 2-meth-- 1,2-diyl-fi-methylene '7 chlorooctadiene-2,7 chlorodecene-l; 2-chlorodecene-1; 2-chlorotetradecene-l; 2-chlorohexadecene-1; 1,2-dichlorohexadecene 1; and 9,10 dichlorooctadecene-l Mixtures of chloro-oleflns and mixtures of chloro-olefins with hydrocarbons or other noninterfering compounds may also be used.

As has been stated hereinbefore, it is essential, inthe present process, to employ reaction conditions that Vary within somewhat narrow limits. Thereaction conditions which must be carefully controlled in order tov achieve good yields of monofluorochloroalkanes by the direct reaction of hydrogen fluoride with chloro-olefins are (1) pressure, (2) proportions of reactants, and (3) reaction time. These three conditions appear to rank. in importance in the order in which they have, been named. For example, hydrogen fluoride and trichloroethylene may be reacted, in a molar ratio of about 7:1, respectively, at210 C.,

at which temperature a minimum of 800 pounds per square inch of pressure is necessary to maintain the reactants in liquid form. However, at 800 pounds per square inch, the yield of monofluorotrichloroethane is insignificant, most of the trichloroethylene being converted into dichlorodifluoroethane. As the pressure is raised, more of the trichloroethylene is converted into the monofluoro derivative, and less into the difluoro derivative. At pressure in excess of 2200 pounds per square inch relatively good yields of the monofluoro derivative are obtained; and, at pressures in excess of 3200 pounds per square inch, forvexample, a pressure of 4400 pounds per square inch, the yield of the monofluoro derivative is much greaterthan the yield of the difluoroderivative, Accordingly, pressures in excess ofabout2200. pounds per. square inch, must belused. Pressures in excess of about 2800 pounds per square inch are preferred, in order toobtainamaximum yield of monofluorochloroalkane, particularly when the contact time is relatively low. In practice, pressures generally will not exceed about 5500 pounds per square inch, but it will be obvious that the process will be operable at pressures higher than about 5500 pounds per square inch.

In the present rocess, it has been found that polyfluorochloroalkanes will be produced to the exclusion of monofluorochloroalkanes if the contact time is extended to six hours or more, unless the pressure is relatively low. Good yields of monofluoroalkanes are obtained, however, even at relatively high pressures when the contact time is about five hours or less. It has also been found that when operating at lower pressures,

i. e., at about 2200 pounds per square inch, a'

maximum contact time of about ten hours is permissible. When a contact time of more than ten hours is used, the reaction proceeds almost exclusively to the production ofpolyfluorochloro- 4 alkanes, regardless of the lowered pressure. Accordingly, the contact time must be less than about ten hours and, preferably, it is less than about five hours. The present process will be operable at very short contact times when the other factors are varied properly. However, a contact time much less than about 30 minutes is not preferred, for practical reasons.

Similarly, the proportions of hydrogen fluoride and chloro-olefin eifect the course of the reaction. when the hydrogen fluoride is present in considerable excess, for example, 2 parts by Weight of hydrogen fluoride per part by weight of trichloroethylene, unless the pressure is extremely high and the contact time is relatively low, the yield of the monofluoro derivative is relatively low. As the proportion of hydrogen fluoride is lowered, for example to a, 1:1 ratio by weight, the yields of the monoiiuoro derivative, at pressures of 2200 pounds per square inch and higher, increase materially. If the proportion of hydrogen fluoride is even further reduced, for example to a l/zzl ratio by weight, the yield of the monofluoro derivative still further increases. weight ratio of hydrogen fluoride to trichloroethylene of 1.5:1 or less is necessary for the production of the monoiiuorochloroalxane product. 'lhe preferred weight ratio is about 1:1. In terms of molar proportions, since trichloroethylene has a molecular weight of about 131 and hydrogen fluoride has a molecular weight of about 20, the above means that a molar ratio of hydrogen fluoride to chloro-olefln reactant of about 13:1 is the upper limit ofpracticability, and that a molar ratio of about 7:1 or lessis preferable. The lower limit of practicable molar ratios is difficult to fix, but generally it may be stated that ratios below 1:1 are impractical. This corresponds to a lower limit in terms of weight ratio of about 0.15:1. With respect to the applicability of the present process to chlorooleflns other than trichloroethylene, it has been found that the proportions'of reactants are best expressed in terms of molar ratio, rather than;

weight ratio. In accordance with the foregoing, the molar ratio of hydrogen fluoride. to chloro-olefln reactant will vary between about. 13:1 and about 1:1, and, preferably, between about 7:1 and about 1:1.

It is to be noted that there is a definite rela.-.

tionship among the three reaction conditions discussed hereinbefore. Failure to control one of In general, the relationship among these reaction,

conditions is as follows: (1) When operating for relatively short contact times, the ratio of reactants and the pressure must be relatively high; i. e., in the upper portion of the ranges of variation for these factors. relatively long contact times, i. e., approaching about ten hours, the ratio of reactants and the pressure must be relatively low. Substantial variation from these limits of variation will generally result in failure to produce the monofluorochloroalkane product, and in almost exclusive production of the polyfluorochloroalkane products.

The temperature of the reaction is not too critical a factor. The success of the present process depends, in the main, on the control of the other reaction conditions as set forth hereinbefore. In general, temperatures below about C. tend to prevent the formation ofmono- Accordingly, it has been found that a (2) When operating for 2,622,106 t fluoro derivatives. Accordingly, temperatures varying between about 200 C. and about 325 C. are satisfactory.

The process may be conducted either batchwise or continuously in suitable equipment, many types of which are well-known to those familiar with the art. Unreacted chloro-oleflns and hydrogen fluoride may be recovered and recycled and by- .Efiect of pressure products may be separated from the desired A series of runs similar to the run set forth monofluoro derivatives by distillation, or by other in Example 1 was made. In this series of runs, well-known means. pressure was varied in conjunction with the con- The following examples will illustrate the detact time and the ratio of the reactants. Pertails and advantages of the process of thisinventinent data for these runs are set forth in Table I.

TABLE I.EFFEOT OF PRESSURE Analysis of the fraction boiling between 6.5-, and 85 C. showed it to contain 65% chlorine and 12% fluorine. The calculated percentages .of chlorine and fluorine in 1,1,2-trichloro-1-fiuoro- 5 ethane are 63.6% and 12.5%, respectively.

EXAMPLES 2, 3, 4, 5 AND 6 Charge, grams 0 Product Analysis on- Run Pressure, Molar ratio, tact Temp.,

p. s. i. HF/C1zC:CHCl time, 0. Volume Volume HF 0120101101 hours percent percent CFzClCHaCl CFCI=CH1C1 tion. In these examples weighed proportions of trichloroethylene and hydrogen fluoride were charged to a high-pressure, rocker bomb which had previously been evacuated. The bomb was heated as rapidly as possible to reaction temperature, maintained there for a specified time, and then allowed to cool. The reactants, upon being released from the bomb through a needle valve, passed through a copper tube into a steel beaker containing ice in ice water. The crude product was water washed, filtered and distilled in a column of ten theoretical plates at a 10:1 reflux ratio. This was a laboratory arrangement and the yields were, therefore, not as good as may be expected from a more carefully designed commercial installation.

EXAMPLE 1 Trichloroethylene and hydrogen fluoride, in the ratio of 505 grams of trichloroethylene to 510 grams of hydrogen fluoride were charged to a high pressure bomb. The bomb and its contents were rocked, heated rapidly to 215 C. and

It will be apparent from Table I that pressure, as stated hereinbefore, is one of the important factors in the reaction involved herein. When operating for periods of time near the upper limit of the contact time range and when using a low ratio of reactants, relatively low pressures are required to give good yields of the monofiuorochloroalkane. However, when the ratio is increased, the desired product is not obtained at low pressures. When operating for relatively short periods of time and at higher ratios, the pressure requirement changes. A relatively low pressure produces a small amount of the desired product, but its yield is increased appreciably when a higher pressure is used.

EXAMPLES 7, 8, 9, 10 AND 11 Efiect of the ratio of reactants Another series of runs was made as in the preceding series, but in this series, the molar ratio of the reactants was varied in relation to the contact time and the pressure. The results and pertinent data for these runs are tabulated in maintained at that temperature for 8 hours. Tam ll.

TABLE II-EFFECT or RATIO OF REAC'TANTS Charge, grams Product analysis Contact Run Molar ratio, Pressure, Temp.,

HF/ClC 01101 s. i. 0. vol HF 0110:0110] p 11mm art3? $8338 3? CFzClCHzCl CFClzCHzCl It will be apparent from the data set forth in Table II that the ratio of reactants is interrelated with the other reaction variables of the reaction. It will be noted that at the lower molar ratios, low pressures and longer reaction periods produce good yields of monofluorochloroalkanes. However, as the ratio is increased to the preferred maximum, the yield falls off to zero. higher ratios of reactants and relatively short contact times are employed, little of the desired product is obtained at relatively low pressures. A ain, at higher pressures, the yields of mono- When ease-ace fluorine-containinge-com'poundsfi For exam-plei they can be dehydrochlorinate'd to produceolefinic fluorides which can, in turn, beconverted to" resins l by polymerization; Also, in I compoun'ds wherein'tthereisarefztwo-i chlorine atom's; one oni.

each. of :two iadj acent carbon atoms, the :chlorine TABLE III-EFFECT OF REACTION TIME" Charge, grams Product analysis Contact Pressure, Molar $81210 Temp., 2 332 5 p. s. i; HFIOliGzCHOl 0. Volume Volume HE. 0130:0110] percent percent GFzClCH2C1 OFChQHzCl increased-to the maximum, a combination of'low ratios of reactantsand relatively low pressures produce good results.

EXAMPLEST2I13; 14,115,16, 1'7 AND 18" Efie'ct .of reaction. temperature A series of runs similar to the run set forth Example 1 was made? In this series or runs;.

temperature was varied in conjunction with contact time; ratio 'of reactants and pressure. The pertinent data are set forth in Table IV.'

atomscan be'removedbytreatment with zinc in alcohol-to produce'olefinic fluorides. This type of reaction is utilizable using the new compounds contemplated herein, namely, the 1,1,2-trichlorol-fiu'oroalkanes.

Although the present invention has been described in conjunction withpreferred embodi-* ments, it is to be understood'that modifications and variationsmay beresorted to without de-' partingfromthe spirit and scope of this 'inven tion, as those skilled in the 'art'will readily .under-'" stand; Such variations "and" modifications are" considered tobe withinith'e scope and purview" What is 'claimed'isz A process. for the production of 1,1,2-tric'hlorol-fluoroethane, which. comprises contacting, hydrogen fluoride with 1,1,2-trichloroethene-1, in a TABLE IVEFFEOT OF REACTION TEMPERATURE Chargagrams. Product analysis Contact Temp., Pressure, Molar ratio 0 0.1 p. s. i. HFICI CICHzCI gag Volume Volume HF CIQCZCHCI percent percent CFiClCHzCl OFC12CH201 It will be apparent from these data thatthe reaction-temperature is not too criticalt'a factor. Goodyields of monofiuo-rochloroalkanes are obtained when relatively low ratios and pressures and relatively long contact times are employed. When, for example, the ratio is increased, an in crease in temperature willnot remedy the disad-' vantageous efiects, and no desired product willibe" obtained. When the pressure is too low, in relation to the ratio and contact time, an increase in temperature iiagain does 1. not: remedy. the disadvantageous. effects. Finally, when-"the ratio is in creased the .use of high" temperatures does not overcomethe undesirable efiect created by this change; On the. other hand, when relatively high pressures and .ratios 'and relatively shorticontact timesLare used, good yields of desired productcan be .attained, whether: the temperature is high or low;

The;monofluorochloroalkanes produced by the molarratio of hydrogen fluoride to said 1,1,2-tri- .ch1or0ethene-l varyinglbetween about 1:1 and about -13E1,at pressures of at least about 2800 pounds per square inch, for a period of time of less than about five hours, and at temperatures varyingf'between'ab-out 200 C. and about 300 C.

WILLIAM A. STOVER.

REFERENCES CITED The following references are of record'in the:

file of thispatent:

UNITED STATES PATENTS N umber Name Date 2,399,024 Harmon Apr. 23, 1946 OTHER REFERENCES Henneet al;, Jour; Am. Chem. Soc, Vol.58,

Grosse-et al., Jour. Org. Chem, vol. 3, pp. 2632-(-1938).'

termediaztes: forzipreparingzxa. large number of- Henne'etal-.,=Ibid., vol: 70', pp. 758-60 (1948-). 

